research communications
Acta Cryst. (2019). E75, 593–599 https://doi.org/10.1107/S2056989019004250 593
Received 11 March 2019
Accepted 28 March 2019
Edited by A. J. Lough, University of Toronto,
Canada
Keywords: crystal structure; dihydrobenzothia-
zine; oxazole; �-stacking; Hirshfeld surface.
CCDC reference: 1906476
Supporting information: this article has
supporting information at journals.iucr.org/e
Crystal structure, Hirshfeld surface analysis andDFT study of (2Z)-2-(2,4-dichlorobenzylidene)-4-[2-(2-oxo-1,3-oxazolidin-3-yl)ethyl]-3,4-dihydro-2H-1,4-benzothiazin-3-one
Brahim Hni,a* Nada Kheira Sebbar,b,a Tuncer Hokelek,c Lhoussaine El Ghayati,a
Younes Bouzian,a Joel T. Magued and El Mokhtar Essassia,e
aLaboratoire de Chimie Organique Heterocyclique URAC 21, Pole de Competence Pharmacochimie, Av. Ibn Battouta, BP
1014, Faculte des Sciences, Universite Mohammed V, Rabat, Morocco, bLaboratoire de Chimie Bioorganique Appliquee,
Faculte des sciences, Universite Ibn Zohr, Agadir, Morocco, cDepartment of Physics, Hacettepe University, 06800
Beytepe, Ankara, Turkey, dDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, and eMoroccan
Foundation for Advanced Science, Innovation and Research (MASCIR), Rabat, Morocco. *Correspondence e-mail:
The title compound, C20H16Cl2N2O3S, is built up from a dihydrobenzothiazine
moiety linked by –CH– and –C2H4– units to 2,4-dichlorophenyl and 2-oxo-1,3-
oxazolidine substituents, where the oxazole ring and the heterocyclic portion of
the dihydrobenzothiazine unit adopt envelope and flattened-boat conforma-
tions, respectively. The 2-carbon link to the oxazole ring is nearly perpendicular
to the mean plane of the dihydrobenzothiazine unit. In the crystal, the molecules
form stacks extending along the normal to (104) with the aromatic rings from
neighbouring stacks intercalating to form an overall layer structure. The
Hirshfeld surface analysis of the crystal structure indicates that the most
important contributions for the crystal packing are from H� � �H (28.4%),
H� � �Cl/Cl� � �H (19.3%), H� � �O/O� � �H (17.0%), H� � �C/C� � �H (14.5%) and
C� � �C (8.2%) interactions. Weak hydrogen-bonding and van der Waals
interactions are the dominant interactions in the crystal packing. Density
functional theory (DFT) optimized structures at the B3LYP/ 6–311 G(d,p) level
are compared with the experimentally determined molecular structure in the
solid state. The HOMO—LUMO behaviour was elucidated to determine the
energy gap.
1. Chemical context
Compounds containing a 1,4-benzothiazine backbone have
been studied extensively both in academic and industrial
laboratories. These molecules exhibit a wide range of biolo-
gical applications indicating that the 1,4-benzothiazine moiety
is a template potentially useful in medicinal chemistry
research and therapeutic applications such as antipyretic
(Warren & Knaus, 1987), anti-microbial (Armenise et al., 2012;
Rathore & Kumar, 2006; Sabatini et al., 2008) , anti-viral
(Malagu et al., 1998), herbicide (Takemoto et al., 1994), anti-
cancer (Gupta & Kumar, 1986) and anti-oxidant (Zia-ur-
Rehman et al., 2009) areas. They have also been reported as
precursors for the syntheses of new compounds (Vidal et al.,
2006) possessing anti-diabetic (Tawada et al., 1990) and anti-
corrosion activities (Ellouz et al., 2016a,b). 1,4-Benzothiazine-
containing compounds are important because of their poten-
tial applications in the treatment of diabetes complications, by
inhibiting aldose reductase (Aotsuka et al., 1994). They are
ISSN 2056-9890
also used as analgesics (Wammack et al., 2002) and and
antagonists of Ca2+ (Fujimura et al., 1996). As a continuation
of our previous work on the syntheses and the biological
properties of new 1,4-benzothiazine derivatives (Sebbar et al.,
2016a,b; Ellouz et al., 2015a,b, 2017a,b), we report herein on
the synthesis and the molecular and crystal structures of the
title compound, (I), along with the Hirshfeld surface analysis
and the density functional theory (DFT) calculations.
2. Structural commentary
The title compound, (I), is built up from a dihydrobenzo-
thiazine moiety linked by –CH– and C2H2– units to 2,4-di-
chlorophenyl and 2-oxo-1,3-oxazolidine substituents,
respectively (Fig. 1). The benzene ring, A (C1–C6), is oriented
at a dihedral angle of 11.27 (6)� with respect to the phenyl ring
D (C15–C20), ring. A puckering analysis of the heterocyclic
portion (ring B; S1/N1/C1/C6–C8) of the dihydrobenzothia-
zine unit gave the parameters QT = 0.1206 (14) A, q2 =
0.1190 (14) A, q3 = �0.0174 (16) A, ’ = 178.2 (8)� and � =
98.4 (8)�, indicating a flattened-boat conformation. A similar
analysis for the oxazolidine ring C (O2/N2/C11–C13) yielded
q2 = 0.1125 (18) A and ’2 = 45.7 (9)�, indicating an envelope
conformation with atom C12 at the flap position and at a
distance of 0.175 (2) A from the best plane of the other four
atoms. The C9/C10 chain C is essentially perpendicular to the
dihydrobenzothiazine unit, as indicated by the C6—N1—C9—
C10 torsion angle of 90.61 (19)�. In the heterocyclic ring B, the
C1—S1—C8 [104.29 (8)�], S1—C8—C7 [121.39 (12)�], C8—
C7—N1 [120.77 (14)�], C7—N1—C6 [126.86 (14)�], C6—C1—
S1 [123.97 (13)�] and N1—C6—C1 [121.60 (15)�] bond angles
are enlarged compared with the corresponding values in the
closely related compounds (2Z)-2-(4-chlorobenzylidene)-4-[2-
(2-oxooxazoliden-3-yl)ethyl]-3,4-dihydro-2H-1,4-benzothia-
zin-3-one, (II), (Ellouz et al., 2017a) and (2Z)-2-[(4-fluoro-
benzylidene]-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzo-
thiazin-3-one, (III), (Hni et al., 2019), and they are nearly the
same as those in (2Z)-4-[2-(2-oxo-1,3-oxazolidin-3-yl)ethyl]-
2(phenylmethylidene)-3,4-dihydro-2H-1,4-benzothiazin-3-
one, (IV), (Sebbar et al., 2016a), where the heterocyclic
portions of the dihydrobenzothiazine units are planar in (IV)
and non-planar in (II) and (III).
3. Supramolecular features
In the crystal, the molecules form stacks extending along the
normal to (104) through �-stacking interactions between
C7 O1 and the C ring at �x + 1, �y + 1, �z + 1
[O1� � �centroid = 3.2744 (16) A, C7� � �centroid = 3.5448 (18) A
and C7 O1� � �centroid = 92.4 (1)�] and between C13 O3
and the C ring at �x + 1, �y + 1, �z [O3� � �centroid =
3.3332 (15) A, C13� � �centroid = 3.4800 (18) A and
C13 O3� � �centroid = 86.7 (1)�] (Figs. 2 and 3). Intercalation
of the aromatic rings between stacks (Fig. 4) leads to an
594 Hni et al. � C20H16Cl2N2O3S Acta Cryst. (2019). E75, 593–599
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Figure 2A partial packing diagram viewed along the a-axis direction with the �-stacking interactions shown by dashed lines.
Figure 1The molecular structure of the title compound with the atom-numberingscheme. Displacement ellipsoids are drawn at the 50% probability level.
overall layer structure with the layers approximately parallel
to (101) (Fig. 3).
4. Hirshfeld surface analysis
In order to visualize the intermolecular interactions in the
crystal of the title compound, a Hirshfeld surface (HS)
analysis (Hirshfeld, 1977; Spackman & Jayatilaka, 2009) was
carried out by using CrystalExplorer17.5 (Turner et al., 2017).
In the HS plotted over dnorm (Fig. 5), the white surface indi-
cates contacts with distances equal to the sum of van der Waals
radii, and the red and blue colours indicate distances shorter
(in close contact) or longer (distinct contact) than the van der
Waals radii, respectively (Venkatesan et al., 2016). The bright-
red spots indicate their roles as the respective donors and/or
acceptors; they also appear as blue and red regions corres-
ponding to positive and negative potentials on the HS mapped
over electrostatic potential (Spackman et al., 2008; Jayatilaka
et al., 2005), as shown in Fig. 6. The blue regions indicate
positive electrostatic potential (hydrogen-bond donors), while
the red regions indicate negative electrostatic potential
(hydrogen-bond acceptors). The shape-index of the HS is a
tool to visualize the �–� stacking by the presence of adjacent
red and blue triangles; if there are no adjacent red and/or blue
triangles, then there are no �ring–�ring interactions. Fig. 7
clearly suggest that there are no �–� interactions in (I).
The overall two-dimensional fingerprint plot, Fig. 8a, and
those delineated into H� � �H, H� � �Cl/Cl� � �H, H� � �O/O� � �H,
H� � �C/C� � �H, C� � �C, H� � �S/S� � �H, C� � �Cl/Cl� � �C, S� � �Cl/
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Acta Cryst. (2019). E75, 593–599 Hni et al. � C20H16Cl2N2O3S 595
Figure 3A partial packing diagram viewed along the b-axis direction with the �-stacking interactions shown by dashed lines.
Figure 4A partial packing diagram viewed along the c-axis direction with the �-stacking interactions shown by dashed lines.
Figure 5View of the three-dimensional Hirshfeld surface of the title compoundplotted over dnorm in the range �0.1152 to 1.5656 a.u.
Figure 6View of the three-dimensional Hirshfeld surface of the title compoundplotted over electrostatic potential energy in the range �0.0500 to 0.0500a.u. using the STO-3 G basis set at the Hartree–Fock level of theory.Hydrogen-bond donors and acceptors are shown as blue and red regionsaround the atoms, corresponding to positive and negative potentials,respectively.
Cl� � �S, O� � �Cl/Cl� � �O, O� � �C/C� � �O and O� � �N/N� � �O
contacts (McKinnon et al., 2007) are illustrated in Fig. 8b–l,
respectively, together with their relative contributions to the
Hirshfeld surface. The most important interaction is H� � �H
(Table 1) contributing 28.4% to the overall crystal packing,
which is reflected in Fig. 8b as widely scattered points of high
density with the tip at de = di = 1.06 A. The pair of the scat-
tered points of wings in the fingerprint plot delineated into
H� � �Cl/Cl� � �H contacts (19.3% contribution to the HS) have a
nearly symmetrical distribution of points, Fig. 8c, with thin
edges at de + di = 2.88 A. The fingerprint plot delineated into
H� � �O/O� � �H contacts (17.0%), Fig. 8d, has a pair of char-
acteristic wings with a pair of spikes with the tips at de + di =
2.48 A. In the absence of C—H� � �� interactions, the pair of
wings in the fingerprint plot delineated into H� � �C/C� � �H
contacts (14.5%) have a nearly symmetrical distribution of
points, Fig. 8e, with thick edges at de + di �2.66 A. The C� � �C
contacts (8.2%), Fig. 8f, have an arrow-shaped distribution of
points with the tip at de = di �1.68 A. Finally, the H� � �S/S� � �H
(Fig. 8g) and C� � �Cl/Cl� � �C (Fig. 8h) contacts (3.7% and 2.9%,
respectively), and are seen as pairs of wide and thin spikes
with the tips at de + di = 3.30 and 3.60 A, respectively.
The Hirshfeld surface representations with the function
dnorm plotted onto the surface are shown for the H� � �H,
H� � �Cl/Cl� � �H, H� � �O/O� � �H, H� � �C/C� � �H, C� � �C and
H� � �S/S� � �H interactions in Fig. 9a–f, respectively.
The Hirshfeld surface analysis confirms the importance of
H-atom contacts in establishing the packing. The large number
of H� � �H, H� � �C/C� � �H, H� � �C/C� � �H and H� � �O/O� � �H
interactions suggest that van der Waals interactions and
hydrogen bonding play the major roles in the crystal packing
(Hathwar et al., 2015).
596 Hni et al. � C20H16Cl2N2O3S Acta Cryst. (2019). E75, 593–599
research communications
Figure 7Hirshfeld surface of the title compound plotted over shape-index.
Table 1Selected interatomic distances (A).
Cl1� � �S1i 3.5625 (7) O3� � �H10B 2.61 (2)Cl2� � �C12ii 3.470 (2) O3� � �H5ii 2.78 (2)Cl2� � �C3iii 3.557 (2) O3� � �H11Bii 2.80 (2)Cl2� � �O2ii 3.3371 (13) O3� � �H9Av 2.73 (2)Cl1� � �H3iv 3.01 (3) O3� � �H9Bv 2.90 (2)Cl1� � �H16i 2.97 (3) O3� � �H11Avi 2.82 (2)Cl2� � �H14 2.51 (2) N2� � �O3vi 3.165 (2)Cl2� � �H4iii 3.12 (2) N2� � �C13vi 3.190 (2)Cl2� � �H12Aii 3.15 (2) N2� � �H9Bv 2.91 (2)Cl2� � �H3iii 2.97 (3) C5� � �C10 3.422 (3)S1� � �N1 3.1231 (14) C7� � �C12v 3.580 (3)S1� � �C16 3.136 (2) C9� � �C13v 3.287 (2)S1� � �H16 2.45 (2) C10� � �C13vi 3.369 (2)O1� � �C10 3.187 (2) C13� � �C13vi 3.320 (2)O1� � �C12ii 3.038 (2) C5� � �H10A 2.97 (2)O1� � �C12v 3.304 (3) C5� � �H9A 2.53 (2)O2� � �C10vi 3.255 (2) C7� � �H10B 2.99 (2)O2� � �C7v 3.143 (2) C8� � �H16 2.99 (2)O3� � �N2vi 3.165 (2) C9� � �H5 2.52 (2)O3� � �C11vi 3.328 (3) C9� � �H9Bv 2.92 (2)O3� � �C11ii 3.375 (2) C10� � �H5 2.92 (2)O3� � �C9v 3.196 (2) C13� � �H9Bv 2.70 (2)O1� � �H12Bii 2.75 (2) C14� � �H12Bv 2.98 (2)O1� � �H9B 2.23 (2) H5� � �H9A 2.06 (3)O1� � �H10B 2.73 (2) H5� � �H10A 2.49 (3)O1� � �H12Aii 2.74 (2) H9A� � �H11B 2.58 (3)O1� � �H12Bv 2.79 (2) H9B� � �H9Bv 2.26 (3)O1� � �H14 2.23 (2) H10A� � �H11A 2.58 (3)O2� � �H10Bvi 2.75 (2) H10B� � �H12Avi 2.45 (3)O2� � �H4ii 2.62 (2) H12A� � �H10Bvi 2.45 (3)
Symmetry codes: (i) �x; yþ 12;�zþ 3
2; (ii) �xþ 1; yþ 12;�zþ 1
2; (iii) x; yþ 1; z; (iv)�x;�y þ 1;�zþ 1; (v) �xþ 1;�yþ 1;�zþ 1; (vi) �xþ 1;�yþ 1;�z.
Figure 8The full two-dimensional fingerprint plots for the title compound,showing (a) all interactions, and delineated into (b) H� � �H, (c) H� � �Cl/Cl� � �H, (d) H� � �O/O� � �H, (e) H� � �C/C� � �H, (f) C� � �C, (g) H� � �S/S� � �H,(h) C� � �Cl/Cl� � �C, (i) S� � �Cl/Cl� � �S, (j) O� � �Cl/Cl� � �O, (k) O� � �C/C� � �Oand (l) O� � �N/N� � �O interactions. The di and de values are the closestinternal and external distances (in A) from given points on the Hirshfeldsurface contacts.
5. DFT calculations
The optimized structure of the title compound, (I), in the gas
phase was generated theoretically via density functional
theory (DFT) using standard B3LYP functional and
6–311 G(d,p) basis-set calculations (Becke, 1993) as imple-
mented in GAUSSIAN 09 (Frisch et al., 2009). The theoretical
and experimental results were in good agreement. The
highest-occupied molecular orbital (HOMO), acting as an
electron donor, and the lowest-unoccupied molecular orbital
(LUMO), acting as an electron acceptor, are very important
parameters for quantum chemistry. When the energy gap is
small, the molecule is highly polarizable and has high chemical
reactivity. The electron transition from the HOMO to the
LUMO energy level is shown in Fig. 10. The HOMO and
LUMO are localized in the plane extending from the whole
(2Z)-2-[(2,4-dichlorophenyl)methylidene]-4-[2-(2-oxo-1,3-
oxazolidin-3-yl)ethyl]3,4-dihydro-2H-1,4- benzothiazin-3-one
ring. The energy band gap [�E = ELUMO � EHOMO] of the
molecule is about 3.42 eV, and the frontier molecular orbital
energies, EHOMO and ELUMO are �5.44 and �2.02 eV,
respectively.
6. Database survey
A search of the Cambridge Crystallographic Database
(Groom et al., 2016; updated to Nov. 2018) using the fragment
II (R1 = Ph, R2 = C; Fig. 11) gave 14 hits with R1 = Ph and R2 =
CH2COOH (Sebbar et al., 2016c), n-octadecyl (Sebbar et al.,
2017a), CH2C CH (Sebbar et al., 2014a), IIa (Sebbar et al.,
2016a), CH2COOEt (Zerzouf et al., 2001), IIb (Ellouz et al.,
2015a), n-Bu (Sebbar et al., 2014b), IIc (Sebbar et al., 2016d),
Me (Ellouz et al., 2015b) and IId (Sebbar et al., 2015). In
addition, there are structures with R1 = 4-ClC6H4 and R2 =
CH2Ph2 (Ellouz et al., 2016c), n-Bu (Ellouz et al., 2017a), IIa
(Ellouz et al., 2017c) and R1 = 2-ClC6H4, R2 = CH2C CH
(Sebbar et al., 2017b). In the majority of these, the heterocyclic
ring is quite non-planar with the dihedral angle between the
plane defined by the benzene ring plus the nitrogen and sulfur
atoms and that defined by nitrogen and sulfur and the other
two carbon atoms separating them ranging from ca 29� in
CH2C CH (Sebbar et al., 2014a), to 36� in IId (Sebbar et al.,
2015), which includes the value of ca 30� for 2H-1,4-benzo-
thiazin-3(4H)-one (WAKLUQ 01; Merola, 2013). The other
three (IIa, IIc and R1 = 4-ClC6H4 and R2 = CH2Ph2; Ellouz et
al., 2016c) have the benzothiazine unit nearly planar with a
corresponding dihedral angle of ca 3–4�. In the case of IIa, the
displacement ellipsoid for the sulfur atom shows a consider-
able elongation perpendicular to the mean plane of the
heterocyclic ring, suggesting disorder, and a greater degree of
non-planarity, but for the other two, there is no obvious source
for the near planarity.
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Acta Cryst. (2019). E75, 593–599 Hni et al. � C20H16Cl2N2O3S 597
Figure 11Related structures.
Figure 9The Hirshfeld surface representations with the function dnorm plottedonto the surface for (a) H� � �H, (b) H� � �Cl/Cl� � �H, (c) H� � �O/O� � �H, (d)H� � �C/C� � �H, (e) C� � �C and (f) H� � �S/S� � �H interactions.
Figure 10The energy-band gap of the title compound.
7. Synthesis and crystallization
Tetra-n-butylammonium bromide (0.1 mmol), 2.20 equiv. of
bis(2-chloroethyl)amine hydrochloride and 2.00 equiv. of
potassium carbonate were added to a solution of (Z)-2-(2,4-
dichlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one
(1.5 mmol) in DMF (25 ml). The mixture was stirred at 353 K
for 6 h. After removal of salts by filtration, the solution was
evaporated under reduced pressure and the residue obtained
was dissolved in dichloromethane. The remaining salts were
extracted with distilled water. The residue obtained was
chromatographed on a silica gel column (eluent: ethyl acetate/
hexane: 3/2). The isolated solid was recrystallized from
ethanol solution to afford colourless crystals [light yellow in
CIF?] (yield: 67%).
8. Refinement
Crystal data, data collection and structure refinement details
are summarized in Table 2. Hydrogen atoms were located in a
difference-Fourier map, and freely refined.
Funding information
The support of NSF–MRI grant No. 1228232 for the purchase
of the diffractometer and Tulane University for support of the
Tulane Crystallography Laboratory are gratefully acknowl-
edged. TH is grateful to the Hacettepe University Scientific
Research Project Unit (grant No. 013 D04 602 004).
598 Hni et al. � C20H16Cl2N2O3S Acta Cryst. (2019). E75, 593–599
research communications
Table 2Experimental details.
Crystal dataChemical formula C20H16Cl2N2O3SMr 435.31Crystal system, space group Monoclinic, P21/cTemperature (K) 150a, b, c (A) 18.4615 (8), 12.8567 (5), 7.9251 (4)� (�) 96.926 (2)V (A3) 1867.33 (14)Z 4Radiation type Cu K�� (mm�1) 4.40Crystal size (mm) 0.21 � 0.12 � 0.05
Data collectionDiffractometer Bruker D8 VENTURE PHOTON
100 CMOSAbsorption correction Numerical (SADABS; Krause et
al., 2015)Tmin, Tmax 0.51, 0.80No. of measured, independent and
observed [I > 2�(I)] reflections14033, 3678, 3252
Rint 0.032(sin �/�)max (A�1) 0.619
RefinementR[F 2 > 2�(F 2)], wR(F 2), S 0.035, 0.093, 1.05No. of reflections 3678No. of parameters 317H-atom treatment All H-atom parameters refined�max, �min (e A�3) 0.37, �0.38
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a),SHELXL2018/1 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012) andSHELXTL (Sheldrick, 2008).
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research communications
Acta Cryst. (2019). E75, 593–599 Hni et al. � C20H16Cl2N2O3S 599
supporting information
sup-1Acta Cryst. (2019). E75, 593-599
supporting information
Acta Cryst. (2019). E75, 593-599 [https://doi.org/10.1107/S2056989019004250]
Crystal structure, Hirshfeld surface analysis and DFT study of (2Z)-2-(2,4-di-
chlorobenzylidene)-4-[2-(2-oxo-1,3-oxazolidin-3-yl)ethyl]-3,4-dihydro-2H-1,4-
benzothiazin-3-one
Brahim Hni, Nada Kheira Sebbar, Tuncer Hökelek, Lhoussaine El Ghayati, Younes Bouzian, Joel
T. Mague and El Mokhtar Essassi
Computing details
Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016);
program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1
(Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for
publication: SHELXTL (Sheldrick, 2008).
(2Z)-2-(2,4-Dichlorobenzylidene)-4-[2-(2-oxo-1,3-oxazolidin-3-yl)ethyl]-3,4-dihydro-2H-1,4-benzothiazin-3-one
Crystal data
C20H16Cl2N2O3SMr = 435.31Monoclinic, P21/ca = 18.4615 (8) Åb = 12.8567 (5) Åc = 7.9251 (4) Åβ = 96.926 (2)°V = 1867.33 (14) Å3
Z = 4
F(000) = 896Dx = 1.548 Mg m−3
Cu Kα radiation, λ = 1.54178 ÅCell parameters from 9952 reflectionsθ = 3.5–72.5°µ = 4.39 mm−1
T = 150 KColumn, light yellow0.21 × 0.12 × 0.05 mm
Data collection
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer
Radiation source: INCOATEC IµS micro–focus source
Mirror monochromatorDetector resolution: 10.4167 pixels mm-1
ω scansAbsorption correction: numerical
(SADABS; Krause et al., 2015)
Tmin = 0.51, Tmax = 0.8014033 measured reflections3678 independent reflections3252 reflections with I > 2σ(I)Rint = 0.032θmax = 72.5°, θmin = 2.4°h = −22→21k = −14→15l = −9→9
Refinement
Refinement on F2
Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.035wR(F2) = 0.093S = 1.05
3678 reflections317 parameters0 restraintsPrimary atom site location: structure-invariant
direct methods
supporting information
sup-2Acta Cryst. (2019). E75, 593-599
Secondary atom site location: difference Fourier map
Hydrogen site location: difference Fourier mapAll H-atom parameters refined
w = 1/[σ2(Fo2) + (0.0467P)2 + 0.9972P]
where P = (Fo2 + 2Fc
2)/3(Δ/σ)max = 0.001Δρmax = 0.37 e Å−3
Δρmin = −0.38 e Å−3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Cl1 −0.02396 (3) 0.92135 (4) 0.75404 (8) 0.05021 (17)Cl2 0.23463 (3) 0.91630 (3) 0.51698 (8) 0.04067 (15)S1 0.17782 (2) 0.48226 (3) 0.53284 (7) 0.03232 (14)O1 0.35726 (7) 0.62658 (10) 0.44041 (18) 0.0330 (3)O2 0.61496 (6) 0.46053 (10) 0.16700 (16) 0.0267 (3)O3 0.54282 (7) 0.59880 (10) 0.19909 (16) 0.0299 (3)N1 0.33467 (7) 0.45458 (11) 0.42952 (18) 0.0227 (3)N2 0.49920 (8) 0.43048 (11) 0.19710 (19) 0.0240 (3)C1 0.21852 (9) 0.36941 (13) 0.4668 (2) 0.0237 (3)C2 0.17612 (10) 0.27967 (14) 0.4671 (3) 0.0298 (4)H2 0.1287 (13) 0.2873 (18) 0.496 (3) 0.036 (6)*C3 0.20375 (10) 0.18467 (15) 0.4260 (3) 0.0328 (4)H3 0.1739 (14) 0.125 (2) 0.424 (3) 0.043 (6)*C4 0.27384 (10) 0.17928 (14) 0.3800 (2) 0.0299 (4)H4 0.2935 (12) 0.1146 (19) 0.352 (3) 0.037 (6)*C5 0.31603 (10) 0.26806 (14) 0.3770 (2) 0.0255 (4)H5 0.3619 (13) 0.2616 (18) 0.342 (3) 0.035 (6)*C6 0.28970 (9) 0.36498 (13) 0.4241 (2) 0.0221 (3)C7 0.31385 (9) 0.55557 (13) 0.4532 (2) 0.0238 (3)C8 0.23937 (9) 0.57999 (13) 0.5014 (2) 0.0233 (3)C9 0.41197 (9) 0.44207 (14) 0.4043 (2) 0.0235 (3)H9A 0.4306 (11) 0.3741 (17) 0.457 (3) 0.029 (5)*H9B 0.4388 (11) 0.4975 (17) 0.468 (3) 0.028 (5)*C10 0.42367 (9) 0.45187 (15) 0.2187 (2) 0.0264 (4)H10A 0.3897 (12) 0.4031 (17) 0.146 (3) 0.031 (5)*H10B 0.4108 (12) 0.5235 (18) 0.181 (3) 0.033 (6)*C11 0.52850 (10) 0.32643 (14) 0.1876 (3) 0.0285 (4)H11A 0.4991 (13) 0.2859 (18) 0.099 (3) 0.038 (6)*H11B 0.5292 (13) 0.2906 (19) 0.295 (3) 0.043 (6)*C12 0.60490 (10) 0.34916 (14) 0.1433 (2) 0.0272 (4)
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sup-3Acta Cryst. (2019). E75, 593-599
H12A 0.6082 (12) 0.3331 (18) 0.024 (3) 0.037 (6)*H12B 0.6420 (13) 0.3167 (19) 0.219 (3) 0.039 (6)*C13 0.54980 (9) 0.50543 (13) 0.1887 (2) 0.0227 (3)C14 0.22602 (9) 0.68205 (14) 0.5250 (2) 0.0246 (4)H14 0.2654 (11) 0.7266 (17) 0.504 (3) 0.027 (5)*C15 0.16331 (9) 0.73590 (13) 0.5785 (2) 0.0241 (4)C16 0.10234 (10) 0.68752 (15) 0.6352 (3) 0.0311 (4)H16 0.0973 (13) 0.612 (2) 0.640 (3) 0.044 (7)*C17 0.04455 (10) 0.74288 (16) 0.6871 (3) 0.0344 (4)H17 0.0037 (15) 0.710 (2) 0.725 (3) 0.050 (7)*C18 0.04662 (10) 0.84994 (16) 0.6841 (3) 0.0330 (4)C19 0.10510 (10) 0.90291 (15) 0.6301 (3) 0.0325 (4)H19 0.1073 (11) 0.9771 (19) 0.626 (3) 0.032 (6)*C20 0.16222 (10) 0.84560 (14) 0.5794 (2) 0.0271 (4)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cl1 0.0335 (3) 0.0432 (3) 0.0774 (4) 0.0150 (2) 0.0207 (3) −0.0079 (3)Cl2 0.0354 (3) 0.0187 (2) 0.0718 (4) −0.00040 (17) 0.0224 (2) 0.0036 (2)S1 0.0250 (2) 0.0169 (2) 0.0593 (3) −0.00047 (16) 0.0225 (2) −0.00057 (19)O1 0.0279 (6) 0.0224 (7) 0.0522 (8) −0.0045 (5) 0.0198 (6) −0.0021 (6)O2 0.0227 (6) 0.0208 (6) 0.0390 (7) −0.0020 (5) 0.0131 (5) −0.0006 (5)O3 0.0380 (7) 0.0183 (6) 0.0349 (7) 0.0008 (5) 0.0106 (5) 0.0001 (5)N1 0.0187 (7) 0.0201 (7) 0.0308 (7) 0.0006 (5) 0.0097 (5) −0.0007 (6)N2 0.0224 (7) 0.0182 (7) 0.0338 (8) −0.0002 (5) 0.0131 (6) −0.0008 (6)C1 0.0231 (8) 0.0175 (8) 0.0316 (9) 0.0011 (6) 0.0080 (7) 0.0013 (6)C2 0.0232 (8) 0.0219 (9) 0.0454 (11) −0.0026 (7) 0.0097 (7) 0.0003 (8)C3 0.0306 (9) 0.0192 (9) 0.0493 (12) −0.0039 (7) 0.0079 (8) −0.0017 (8)C4 0.0323 (9) 0.0187 (9) 0.0395 (10) 0.0027 (7) 0.0070 (8) −0.0039 (7)C5 0.0252 (8) 0.0221 (9) 0.0304 (9) 0.0036 (7) 0.0083 (7) −0.0007 (7)C6 0.0220 (8) 0.0183 (8) 0.0268 (8) −0.0015 (6) 0.0060 (6) 0.0008 (6)C7 0.0225 (8) 0.0186 (8) 0.0320 (9) −0.0007 (6) 0.0105 (7) 0.0000 (7)C8 0.0212 (8) 0.0187 (8) 0.0319 (9) −0.0005 (6) 0.0103 (6) 0.0012 (6)C9 0.0167 (7) 0.0272 (9) 0.0274 (8) 0.0014 (7) 0.0063 (6) −0.0011 (7)C10 0.0219 (8) 0.0298 (10) 0.0287 (9) 0.0022 (7) 0.0079 (7) 0.0010 (7)C11 0.0294 (9) 0.0171 (8) 0.0412 (10) −0.0003 (7) 0.0137 (8) 0.0007 (7)C12 0.0280 (9) 0.0189 (8) 0.0365 (10) 0.0015 (7) 0.0116 (8) −0.0030 (7)C13 0.0257 (8) 0.0212 (8) 0.0224 (8) −0.0008 (7) 0.0085 (6) 0.0008 (6)C14 0.0217 (8) 0.0193 (8) 0.0346 (9) −0.0008 (7) 0.0109 (7) 0.0007 (7)C15 0.0229 (8) 0.0206 (8) 0.0299 (9) 0.0021 (6) 0.0075 (7) 0.0005 (7)C16 0.0265 (9) 0.0236 (9) 0.0456 (11) −0.0001 (7) 0.0143 (8) −0.0021 (8)C17 0.0255 (9) 0.0330 (10) 0.0475 (12) 0.0011 (8) 0.0155 (8) −0.0029 (8)C18 0.0255 (9) 0.0328 (10) 0.0416 (10) 0.0085 (8) 0.0087 (8) −0.0040 (8)C19 0.0311 (10) 0.0226 (9) 0.0445 (11) 0.0062 (7) 0.0070 (8) −0.0002 (8)C20 0.0250 (8) 0.0219 (9) 0.0353 (9) 0.0019 (7) 0.0070 (7) 0.0010 (7)
supporting information
sup-4Acta Cryst. (2019). E75, 593-599
Geometric parameters (Å, º)
Cl1—C18 1.7385 (19) C7—C8 1.504 (2)Cl2—C20 1.7373 (18) C8—C14 1.352 (2)S1—C8 1.7321 (17) C9—C10 1.518 (2)S1—C1 1.7430 (17) C9—H9A 1.01 (2)O1—C7 1.227 (2) C9—H9B 0.97 (2)O2—C13 1.364 (2) C10—H10A 1.01 (2)O2—C12 1.453 (2) C10—H10B 0.99 (2)O3—C13 1.211 (2) C11—C12 1.522 (2)N1—C7 1.374 (2) C11—H11A 0.98 (2)N1—C6 1.418 (2) C11—H11B 0.97 (3)N1—C9 1.473 (2) C12—H12A 0.97 (2)N2—C13 1.349 (2) C12—H12B 0.95 (2)N2—C11 1.448 (2) C14—C15 1.455 (2)N2—C10 1.451 (2) C14—H14 0.96 (2)C1—C2 1.394 (2) C15—C16 1.406 (2)C1—C6 1.397 (2) C15—C20 1.411 (2)C2—C3 1.378 (3) C16—C17 1.386 (3)C2—H2 0.94 (2) C16—H16 0.97 (3)C3—C4 1.388 (3) C17—C18 1.377 (3)C3—H3 0.94 (3) C17—H17 0.95 (3)C4—C5 1.384 (3) C18—C19 1.387 (3)C4—H4 0.94 (2) C19—C20 1.385 (3)C5—C6 1.404 (2) C19—H19 0.96 (2)C5—H5 0.93 (2)
Cl1···S1i 3.5625 (7) O3···H10B 2.61 (2)Cl2···C12ii 3.470 (2) O3···H5ii 2.78 (2)Cl2···C3iii 3.557 (2) O3···H11Bii 2.80 (2)Cl2···O2ii 3.3371 (13) O3···H9Av 2.73 (2)Cl1···H3iv 3.01 (3) O3···H9Bv 2.90 (2)Cl1···H16i 2.97 (3) O3···H11Avi 2.82 (2)Cl2···H14 2.51 (2) N2···O3vi 3.165 (2)Cl2···H4iii 3.12 (2) N2···C13vi 3.190 (2)Cl2···H12Aii 3.15 (2) N2···H9Bv 2.91 (2)Cl2···H3iii 2.97 (3) C5···C10 3.422 (3)S1···N1 3.1231 (14) C7···C12v 3.580 (3)S1···C16 3.136 (2) C9···C13v 3.287 (2)S1···H16 2.45 (2) C10···C13vi 3.369 (2)O1···C10 3.187 (2) C13···C13vi 3.320 (2)O1···C12ii 3.038 (2) C5···H10A 2.97 (2)O1···C12v 3.304 (3) C5···H9A 2.53 (2)O2···C10vi 3.255 (2) C7···H10B 2.99 (2)O2···C7v 3.143 (2) C8···H16 2.99 (2)O3···N2vi 3.165 (2) C9···H5 2.52 (2)O3···C11vi 3.328 (3) C9···H9Bv 2.92 (2)O3···C11ii 3.375 (2) C10···H5 2.92 (2)
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sup-5Acta Cryst. (2019). E75, 593-599
O3···C9v 3.196 (2) C13···H9Bv 2.70 (2)O1···H12Bii 2.75 (2) C14···H12Bv 2.98 (2)O1···H9B 2.23 (2) H5···H9A 2.06 (3)O1···H10B 2.73 (2) H5···H10A 2.49 (3)O1···H12Aii 2.74 (2) H9A···H11B 2.58 (3)O1···H12Bv 2.79 (2) H9B···H9Bv 2.26 (3)O1···H14 2.23 (2) H10A···H11A 2.58 (3)O2···H10Bvi 2.75 (2) H10B···H12Avi 2.45 (3)O2···H4ii 2.62 (2) H12A···H10Bvi 2.45 (3)
C8—S1—C1 104.29 (8) C9—C10—H10A 110.3 (12)C13—O2—C12 109.43 (13) N2—C10—H10B 109.8 (13)C7—N1—C6 126.86 (14) C9—C10—H10B 108.4 (13)C7—N1—C9 114.42 (14) H10A—C10—H10B 107.1 (17)C6—N1—C9 118.72 (14) N2—C11—C12 101.36 (14)C13—N2—C11 113.07 (14) N2—C11—H11A 110.5 (13)C13—N2—C10 123.45 (15) C12—C11—H11A 112.7 (14)C11—N2—C10 123.45 (14) N2—C11—H11B 111.1 (14)C2—C1—C6 120.75 (16) C12—C11—H11B 112.3 (14)C2—C1—S1 115.20 (13) H11A—C11—H11B 108.8 (19)C6—C1—S1 123.97 (13) O2—C12—C11 105.47 (13)C3—C2—C1 120.61 (17) O2—C12—H12A 108.2 (14)C3—C2—H2 122.4 (14) C11—C12—H12A 110.6 (13)C1—C2—H2 117.0 (14) O2—C12—H12B 106.3 (14)C2—C3—C4 119.33 (17) C11—C12—H12B 112.9 (14)C2—C3—H3 119.4 (15) H12A—C12—H12B 113.0 (19)C4—C3—H3 121.2 (15) O3—C13—N2 128.64 (16)C5—C4—C3 120.53 (17) O3—C13—O2 122.07 (15)C5—C4—H4 119.3 (14) N2—C13—O2 109.30 (14)C3—C4—H4 120.1 (14) C8—C14—C15 131.80 (16)C4—C5—C6 120.93 (16) C8—C14—H14 113.7 (13)C4—C5—H5 117.9 (14) C15—C14—H14 114.5 (13)C6—C5—H5 121.2 (14) C16—C15—C20 115.34 (16)C1—C6—C5 117.79 (15) C16—C15—C14 125.33 (16)C1—C6—N1 121.60 (15) C20—C15—C14 119.31 (16)C5—C6—N1 120.60 (15) C17—C16—C15 122.84 (18)O1—C7—N1 119.71 (15) C17—C16—H16 114.8 (15)O1—C7—C8 119.48 (15) C15—C16—H16 122.4 (15)N1—C7—C8 120.77 (14) C18—C17—C16 118.95 (18)C14—C8—C7 115.16 (15) C18—C17—H17 118.7 (16)C14—C8—S1 123.40 (13) C16—C17—H17 122.4 (16)C7—C8—S1 121.39 (12) C17—C18—C19 121.36 (17)N1—C9—C10 112.06 (14) C17—C18—Cl1 119.91 (15)N1—C9—H9A 109.0 (12) C19—C18—Cl1 118.70 (15)C10—C9—H9A 113.1 (12) C20—C19—C18 118.45 (18)N1—C9—H9B 106.8 (12) C20—C19—H19 118.9 (13)C10—C9—H9B 108.7 (12) C18—C19—H19 122.7 (13)H9A—C9—H9B 106.9 (16) C19—C20—C15 123.05 (17)
supporting information
sup-6Acta Cryst. (2019). E75, 593-599
N2—C10—C9 110.45 (14) C19—C20—Cl2 116.31 (14)N2—C10—H10A 110.7 (12) C15—C20—Cl2 120.64 (13)
C8—S1—C1—C2 −175.06 (14) C11—N2—C10—C9 81.1 (2)C8—S1—C1—C6 8.14 (18) N1—C9—C10—N2 −175.21 (14)C6—C1—C2—C3 0.3 (3) C13—N2—C11—C12 −8.6 (2)S1—C1—C2—C3 −176.63 (16) C10—N2—C11—C12 173.17 (16)C1—C2—C3—C4 −1.5 (3) C13—O2—C12—C11 −10.95 (19)C2—C3—C4—C5 0.6 (3) N2—C11—C12—O2 11.27 (19)C3—C4—C5—C6 1.5 (3) C11—N2—C13—O3 −177.18 (18)C2—C1—C6—C5 1.8 (3) C10—N2—C13—O3 1.1 (3)S1—C1—C6—C5 178.44 (13) C11—N2—C13—O2 2.2 (2)C2—C1—C6—N1 −177.45 (16) C10—N2—C13—O2 −179.56 (15)S1—C1—C6—N1 −0.8 (2) C12—O2—C13—O3 −174.76 (16)C4—C5—C6—C1 −2.7 (3) C12—O2—C13—N2 5.81 (18)C4—C5—C6—N1 176.56 (16) C7—C8—C14—C15 −176.93 (18)C7—N1—C6—C1 −9.1 (3) S1—C8—C14—C15 0.3 (3)C9—N1—C6—C1 172.24 (16) C8—C14—C15—C16 6.6 (3)C7—N1—C6—C5 171.68 (17) C8—C14—C15—C20 −175.08 (19)C9—N1—C6—C5 −7.0 (2) C20—C15—C16—C17 0.6 (3)C6—N1—C7—O1 −173.69 (16) C14—C15—C16—C17 179.02 (19)C9—N1—C7—O1 5.0 (2) C15—C16—C17—C18 −0.3 (3)C6—N1—C7—C8 8.7 (3) C16—C17—C18—C19 0.1 (3)C9—N1—C7—C8 −172.58 (15) C16—C17—C18—Cl1 −178.22 (16)O1—C7—C8—C14 0.9 (3) C17—C18—C19—C20 −0.3 (3)N1—C7—C8—C14 178.52 (16) Cl1—C18—C19—C20 178.04 (15)O1—C7—C8—S1 −176.37 (14) C18—C19—C20—C15 0.7 (3)N1—C7—C8—S1 1.2 (2) C18—C19—C20—Cl2 −178.85 (15)C1—S1—C8—C14 174.78 (16) C16—C15—C20—C19 −0.8 (3)C1—S1—C8—C7 −8.17 (17) C14—C15—C20—C19 −179.34 (18)C7—N1—C9—C10 −88.22 (19) C16—C15—C20—Cl2 178.68 (14)C6—N1—C9—C10 90.61 (19) C14—C15—C20—Cl2 0.2 (2)C13—N2—C10—C9 −97.0 (2)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, y+1, z; (iv) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y+1, −z.